Plastic composition and method of preparing the same.



; Jones Age-s arms, orLEAsnonAnGE,

No Original NEW JERSEY, ASSIGNOR OF ONE-HALF TO 7' FRANK n- DYER, orMON'ICLAIB, NEW JERSEY.

I frnes'rfccomrosriuon Ania METHOD or PREPARINGTHE SAME.

Tofdll whom Lt monomers; -Be it known that I, Jomxs Artswon rn,

a citizen vof the United- States,- and, a resident of East Grange, inthe county of Essex and- State of New Jersey, have made a oer tain newand useful. Inventionin Plastic Composition; and Methods of.Preparing'the Same, of which 'thefollowing is adescrip plication, Sen;

This application is'a division of my ap No. 543,238,. filed .Feb. 11,

' 1910, entitledphenoliccondensation product and method of preparingsame,

March 19,1912, No.- 1,020,593. The said ap- I patented plication"relates, to infusibleycondensation products of phenol and substancescontain 'ingthe methylene radical, CH and meth- Ode of preparingthesame. Therein are described products '20 formed" by combining a fusibleresinous phenolic condensation prod- 1 not with amethylene-amincompound, and'a fmethod of producing-the same, modifiedproducts and processes; in 5 solidsolutions of the-=firstnamed products.'25-' and; also which with various described substances are formed. Insome instances the last mentioned substances have the function offixingor combining with ammonia, int'he product.

This application, relates to allof the said solid solution products andprocesses, "and the obj ect of this invention, asclainied herein, is toproduce compositions of the ter referred-to, having new and useful characteristics,and todevise .a method for pre- 3 paring the same, as willbe hereinafter more particularly described,

the appendedclaims.

9 In my application- SeriahNo 196,060,

-.- composition and process, for manufacturing the same, .filed May.:14,- 1909, I describe an ultimate infusible insoluble conden'satlon.

product of phenol and "formaldehyde: 'or

. their equivalents,'which is prepared by first forming a fusible.condensation product of phenol and formaldehyde, 'n which the alde hyde'is all combined with the phenol, and

' the phenol is all, or nearly all,,combined polymerized form offormaldehyde, an

' an amount of the fusible condensation product and any i :with thealdehyde, and: then causinga further reaction between the same and anaddi of ans-aldehyde, preferabliygaf tional amount I in just' suflicientto combine with all Specification of Letters lfatent.

char-e9 and pointed out Patented Dec. 3, 1912.

ppli cation filed February 11, 1-91o,seria1 No. 548,238. Divided andthis applicatibnfi1d-0ctoher7, 1911. Serial 'No. 653,402

free phenol contained therein,to form the desired ultimate infusiblecondensation product. In my Patent Nb. 1,020,593, of which this ,is 'adivision, I describe a product formed by combining a fusible anhydrousresinous condensation product of a phenol and an aldehyde with amethylene amin compound, such' as heXa-methyleneamin, or hexamethylene-.tetra-amin as it is sometimes called (CH N .,O1" in place of thelatter, the mixture of salts obtained by the comand-formaldehyde mightbe used. lhe fusi- Jble' anhydrous resinous condensatiorfproductreferred to above, (hereafter termed a phenol resin is first prepared bycausing a reaction between suitable amounts of phenol and formaldehydeor their equivalents without the aid of any. catalytic or condensingagent, as described in my application Ser. No. 496,060 above referredto. This operation is conducted in such a manner that a fusibleanhydrous resinresults, which is thinly fluid When molten, the resinbeing completely dehydrated, after the condensa- 'ti'on reaction,b'yheatin' to a sufficient temperature, as 400 F, undcr atmosphericpres- ,heating to such a fusible resin. This dehydrated resin is 'mixedwith a methylene-amin compound, also anhydrous, in definite proportions,forming a mass which is fluid at temperagre'es F, and, which, whenmaintained at these temperatures or higher temperatures fora short time,Will'harden to a hard infusible chemically inert mass. This ulti- -matecondensation product possesses great tensile strengthGounteractingpressure need not be used during the reaction be-. tweenthefusible condensation product and the methylene-amin compound, and thisreaction is. not accompanied by evolution of formaldehyde, Water, orother gaseous products, which,

porousand useless, for many purposes.

, It will be seen that the process thus far disclosed differs fromtheprocess for form-. ing an infusible phenolic condensation prodbinationof aqueous solutions of ammoniatur e's between 200 degrees F. and 240 de'f evolved, would bubble through the mass and render the product sure.vAs isstated in the said application, i temperature drives'ofi' all;the'w'ater, both free and combined, from the '105 7 not disclosed in myapplication Ser. No.

. heat.

496,060, above referred to, broadly by the substitution of amethylene-amin compound for the paraformaldehyde or other polymerizedformaldehyde, which, in my previous invention, I combine with thefusible phenol resin to form the ultimate condensation product. I havefound that the methyleneamm is superior to tn aldehyde for addi-- tionto the phenol resin for hardening the mass, for a number of reasons. Ithas no tendency to cause foaming of the mass even if an excess ofmethylene-amin is used above the amount which I have discovered to benecessary to combine with all of the phenol resin to harden the same.Paraformaldehyde or .otheraldehyde added to the phenol resin in myprevious invention tends to escape as gas if an excess is used above theamount necessary .to combine all of the phenol resin, or if the finalreaction is carried on too speedily'or under too intense a, In the caseof the amin compound, however, there is no free formaldehyde and themethylene radical can only be separated from the nitrogen by its beingtakenaway from the same by reaction with the phenol resin with which itcombines in exchange.

for some of the hydrogen of the resin which .unites with the nitrogen,to form ammonia. Methylene never exists in the free state, and hence themethylene-amin used cannot cause bubbling or gassing. Therefore, when.the methylene-amin is used, great care need not be taken to prevent theadditiqn of a slight excess of this element to prevent foaming of themass.

Another advantage of the methylene-amin compound over theparaformaldehyde for the function referred to is that it will cause ahardening of the mass at a much lower temperature than will theparaformaldehyde.

' hardens and becomes infusible. This phenol resin or fusiblecondensation product of phenol and formaldehyde is apparently dn oon omoorn n o o6Hbo CH2 CaH4O CH3 C'eHs That is, approximately two parts offormaldehyde are caused to combine with three parts of phenol bymolecular Weight. Two molecules of formaldehyde apparently combine withthree molecules of phenol in the manner indicated with the evolution oftwo molecules of water. This formula'gives a molecular weight for thefusible product of 306, which checks up quite well with thedetermination of the weight made by physical means, indicating that themolecule cannot be of double molecular weight or any other multiple ofthe weight here shown when prepared with pure ingredients and at Inpractical oper proper temperatures. ations, however, such care as topurity and temperature is not essential to obtain a product suitable forthe use herein mentioned, and such phenol resin products may bea mixtureof the above compositions with others of higher molecular weight due topolymerization or to decomposition from long treating at hightemperature.

To produce the final product, I combine 100 parts by weight of thefusible anhydrous pure phenol resin with from 7.6 to 12 parts of'hexa-methylene-tetra-amin at a temperature of preferably 220 degrees F.,together with the ammonia-fixing, or other solid solvent or plasticityagent, as will be hereinafter described; The proportions require to bevaried within the limits indicated, because the fusible resin sometimescontains more or less free phenol, which should be combined with themethylene radical of the methylene amin to produce the final infusibleproduct. This is in agree ment with the following equation:

CaHaO CHg 6 \C5H4O +(canmFs oseroonnwms This reaction. causes theformation of an infusible refractory resinous amorphous mass of paleyellowish amber color when the reacting substances are pure. The ammoniaradical, N H is retained in the mass in unstable combination and partmay be removedby pulverizing and warming.

' Half ofthe ammonia. is liberated from the roduct at about 260 degreesF. if it is ormed in thin films to facilitate the removal of theammonia, and at 340 degrees F. practically'all of theammonia is evolved.It 1s, however, not practicable to so treat all objects to remove .theammonia by simple heat treatment, and even when such heat treatment isresorted to, the result is not the complete elimination ofthe ammonia,and considerable internal stresses may be set up, which are likely tocause cracks and warping in the product. If ammonia is not removed itremains either imprisoned in the intermolecular spaces of the mass, orin loose combination therewith. This-product may cause corrosion ofcertain metals when it is used in contact with them, and on account ofits tendency to absorb traces of'water, the

otherwise excellent insulating qualities of the product are impaired. Toovercome these objectionable features, I-prefer to add to the massbefore hardening, a'substance which will combine with and fix theaminonia and render it a permanent harmless con stituent of the product.The substances which I find as a class to be satisfactory for thispurpose are the organic acid anhydrids;

Those which I find particularly well suited for the purpose are theanhydrids of the higher members of the series acetic series, as itisoftencalled, and also benzoic and phthalic anhydrid. The action of anyof these substances is to combine with which remain in theproductas asolid solvent of the same. This process and product are claimed herein..

The anhydrids of the organic acids are effective when used in amountsnecessary to fix all or part of the ammonia in the prodme, For mostpurposes, one-half the amount necessary to combine with the ammonia issuflicient, as a part of the ammonia is retained so' tenaciously withinthe substance as to be unobjectionable. If any traces of moisture arepresentin the ingredients, they are eflectively fixed by theacidanhydrid. It should also be noted that if any free phenol is present inthe" fusible resin to which the methylene-amin compound .and the acidanhydrid are added, it may be combined with the acid anhydrid to form aphenyl ester. e

If benzoic anhydrid is used, the proportion should be about: phenolresin 100 parts, hexa-methylene-tetra-amin 7 .6 to 12 parts, benzoicanhydrid 4 to 9 parts. llf

'stearic anhydrid is used, the proportion should be about: phenol resin100 parts, hexa-methylene-tetra-amin 7.6 to 12 parts,

' stearic anhydrid 9 to 15 parts. The proportions vary slightly if otherof the ammonia fixing'agents mentioned are'used, as may be determmed byexperiment. The amount of whatever anhydrid is used depends more or lessupon'the molecular weight of the particular anhydrid used. If thestearic anhyacid anhydrid is added to themass it per-'- forms a triplefuncton, namely, to fix the drid is used, it should be noted that thissubstance does not perfectly dissolve in the amount of phenol resinrequired, so, therefore, it is advisable to add a small amount of asubstance which will cause the 'stearic "anhydrid to emulsify or becomemiscible.

The acid amid of stearic or other fatty acid is suitable when added insmall amounts. It should be noted that when an organic tion when hot orcold.

(3,11 ,10 or the heated to take an impression vious application, Ser.ferred to. I may also use ammonia, to fix any traces of moisture whichmay be present in the ingredients, and to act as a solid solvent orplasticity agent for the final product.

As I stated in the specification of my previous application referred to'Ser. No. 496,060, I define a finalproduct solvent as a substance whichwill dissolve the ultimate condensation p'rodu-ctior combine therewithat the baking temperature, render it plastic at-such temperature andremain as a part of the product in the condition of solid solu- Any ofthe solid solvents referred to in the above mentioned application may be.usedin place of the organic acid anhydrid when it is not deemednecessary to fix the ammonia in the composition. Thus, I-may 'usenaphthalene'and some of its derivatives such as nitro'and chloroderivatives, espe cially the mono-nitro and di-nitro and monochloronaphthalenes, di-nitro benzene, preferably the meta variety, acetanilid,r1c1- 'noleic acid, ricinela'idic acid, and their anhydrids, and diphenylamin in suitable proportions, as described in my application abovereferred to.

It is obvious that the mass may have incorporatedv therewith any of thevarious fibrous or inert powdered substances as fillers, and alsopigments as desired.

*' I do not-limit the invention to the particular methylene-amincompound specifically referred to, the heXa-methylene-tetraamin beinggiven for the purpose of definite description, since it is a wellknownsubstance, which may readily be obtained in the pure state, othermethylene-amins, such as the substance produced by the action of liquidammonia on formaldehyde or its polymers in various proportions givingequally good results. If desired an, acid amid of one of the highermembers of acetic series of acids maybe formed and added to theingredients, instead of adding the corresponding acid anhydrid andforming the amid within the mass'by reaction between the anhydrid andthe contained ammonia. My ultimate product is particularly useful whenit contains a suitable acid amid, either formed by the-interaction ofthe added acid anhydrid with the ammonia within" the mass, or previouslyformed and added as a separate'ingredient, as described, because theamid acts as a solid solvent and renders the mass sufiiciently plasticwhen from a die or mold. This effect was described in connectio n witlr"the description of the functions ofthe product solvent elements in mypre- No. 496,060 above rean excess of-the fusible phenol resin vas asolid solvent if I desire. In that case, an amount of the themethylene-amin' less than the amount nec essa-ryto combine with-quiteall ofthe fusi- 'ble phenol resin would be "addedto the latter, so thatunconibinedphenol resin, of an amount about-equal to that of the; othersolid solvent'elements referred to, would be provided for acting as asolid solvent for ';-=In1 my application, SerJNo. 630,893, 10

the ultimate product.

filed June 2','1911',upon ,which Patent'No. 1,020,594

- was granted-.Mafi- 19, 1912, is described a process and product-inwhich an organic acid or its; anhy'dr-id,'."specifically phth'alic acidor -'anhydrid, islused as the sold solvent orf plasticity a cut, Thatapplication isgeneric to aproduct inadewith either [formaldehyde orpolymer,'; be hem-methyl? ene-tetra-amin', as the methylene-containingharden ng'agent, and contains Zlfi-IIIIS specific to'tlie formaldehydespecies, This application-is specific to a process in 'which hexa-nethylene-tetra-amin isused, or am-- monia is included in the mass,during reaction, the solid solvent or plasticity.agent.

being claimed generically in the'product and process claims, and alsospecifically as fan ammonia-fixing element.

I understood as including In the claims, the gterm phenol? is tobeotherequivalents" of. p enol, such as;'creso1,.

and the-term formaldehyde. is tofbe .un-

derstood as including the polymers of for maldehyde.' Having nowdescribed myainvention what 'I claim and desire to secure by Letters'Patent is.':t

1. The process of forminga hard Ycon densation product which consists inincor porating a fusible phenolic condensation product .with.hexa-methylene-tetra=amin, and a final product solventelement, and

heating the mixt u re" sufliciently'to harden theinass, substantially asdescribed.

2. The process. of forming a hard: condensation product which consistsinincorporatproduct formed byheating the mass at suf: ficienttemperature andyre'nders the product plastic at such temperature, andheating the mixture sufficiently stantiallyas. described.

The process of forming a hard con-' "densation product which consists ininproduct with hexa met'hylene-tetra-amin,

and a Isolid-acid anhydrid of the acetic series, and heating the mixturesufiicientl-y to harden scribed.- I

4'. Theprocess of forming-a hard condenthe homologues and.

'to ingredients including phenolic to harden the mass, subthe .mass,substantially as de-.'

noaaeao 'sation product which consists in incorporat- 7 ing; with afusible phenolic condensation product hexa-methylene-tetra-amin indefinite proportions and ingredients for fixing ammonia, and formingasolid solvent for the final product, and heating the mass to harden thesame and fix free ammonia, sub- I stantially as described.

"5. The process of forming a hard condensa-tion product which conslsts1n 1ncorporating with a fusible phenolic condensation pro-ducthexa-methylene-tetra-amin in some. ofthe same to be combined with theammoniafixing element, substantially as described 6. In a process forforming an infusible phenolic condensation product, the step whichconsists in adding an ammonia-fixing, solid solvent, element, toingredients suit-able to produce such product by reaction, and whichinclude ammonia during such reaction, substantially as described.

Z The'process of forming an infusible phenolic condensation product,which con- Sists in adding an ammonia-fixing solid solvent, element, toingredients including phenolic and methylene containing bodies, which"ingredients, during subsequent reaction, also contain ammonia, andheating :the mass to cause such reaction and accordingly to form thesaid 'tially as described.

product, substan- 8. The process of forming an infusible phenoliccondensation product which consistsin adding an organic acid anhydrldand methylene containing bodies, which ingredients during subsequentreaction also contain ammonia and heating the mass to cause suchreaction and accordingly to form the said product, substantially asdescribed.

9. As a new composition of matter, a final condensation product ofmethylene and phenol, or a homologue or derivative of phenol, andcontaining an organic acid amid subStantially as descrlbed.

hard infusible product formed by the combination under sufiicient heatof a fusible solvent element, substantially as described. corporating afusible phenolicc'ondensation 11. As'a new composition of matter, the

10. 'As a new composition of matter, the

bination under sufiicient heat of a fusible phenolic condensationproduct with hexamethylene-tetra-amin, and an organic acid anhydrid,substantially as described.

l2p-As a new composltionof matter, a

final condensation product of methylene and methylene-tetra-amin, and anammonia fix- 10 phenol, or a homologue or derivative of ing element,substantially as described. phenol, and containing an organic acid Thisspecification signed and witnessed amid and phenyl ester, substantiallyas dethis 3d day of October, 1911.

5 scribed.

18. As a new composition of matter, the JONAS AYLSVVORTH' hard infusibleproduct formed by the com- Witnesses: bination under suflicient heat ofa fusible DYER SMITH,

phenolic condensation product With hexa- KIRK BROWN.

